Separation Science and Technology, 50: 886–891, 2015
Copyright © Taylor & Francis Group, LLC
ISSN: 0149-6395 print / 1520-5754 online
DOI: 10.1080/01496395.2014.966204
Preparation of High Surface Area Activated Carbon from
Elaeagnus angustifolia Seeds by Chemical Activation with ZnCl2
in One-Step Treatment and its Iodine Adsorption
Ömer Şahin,1 Cafer Saka,2 Ayhan Abdullah Ceyhan,3 and Orhan Baytar3
1
Faculty of Engineering and Architecture, Siirt University, Siirt, Turkey
2
School of Health, Siirt University, Siirt, Turkey
3
Faculty of Engineering and Architecture, Selcuk University, Konya, Turkey
The present study was conducted with the preparation of acti-
vated carbon through one-step chemical activation using zinc chlo-
ride (ZnCl2 ) as the activating agent from Elaeagnus angustifolia
seeds (EAS). The effect of impregnation ratio, activation temper-
ature, and activation time on activated carbon surface area was
discussed. The properties of activated carbon were characterized
by N2 adsorption (BET), thermogravimetric analyses (TGA), scan-
ning electron microscopy (SEM), and Fourier transform infrared
spectroscopy (FTIR). The best conditions for preparing activated
carbon were identified to be temperature of 500◦ C, impregnation
ratio of 150%, impregnation time of 48 h, and activation time
of 60 min with BET surface area of 1836 m2 /g. The adsorption
capacity was demonstrated by the iodine numbers.
Keywords activated carbon; Elaeagnus angustifolia seeds; chemical
activation; one-step pretreatment
INTRODUCTION
Activated carbon with highly developed surface area is a
well-known material used in the purification of gases, the
removal of organic pollutants from water (i.e., purification of
drinking water and wastewater), the removal of heavy metal
from wastewater due to its efficiency, and economic feasibil-
ity (1). Utilization of activated carbon can be in the form of
powder, granular, and fiber or cloth. The world demand for acti-
vated carbons vary, being around 1.1 million tons per annum,
and growing at 9% p.a., and it is expected to increase more than
10% per year over the next 5 years (2). As a result, the cost of
activated carbon is also growing depending on the application.
Designing ways for the production of activated carbon through
economic ways is the need of the hour.
Received 13 April 2014; accepted 12 September 2014.
Address correspondence to Cafer Saka, School of Health, Siirt
University, 56100 Siirt, Turkey. E-mail: sakaca1976@gmail.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsst.
886
Their textural and adsorptive properties depend on the pre-
cursor, the activation process used, chemical or physical, the
number of steps, the activating agents, the time of gasification,
and the oxidation process. Raw materials for the produc-
tion of activated carbon are chosen depending on their price,
purity, potential extent of activation, and stability of supply.
Commercial activated carbons are mainly produced from wood,
coal, and coconut shell. However, commercially available acti-
vated carbon is expensive. Therefore, many studies have been
performed on the development of low-cost activated carbons
from various agricultural by-products or wastes, such as pis-
tacchio shell (3), cotton stalks (4), acorn shell (5, 6), bagasse
and rice husk (7), corn cob (8), safflower seed press cake (9),
the vetch (10), Elaeagnus angustifolia seeds (11), barley husks
(12), nutshells (13), wood sawdust (14), jackfruit peel (15), rice
husks (16), etc.
In principle, the methods for preparing the activated car-
bons can be divided into two categories: physical activation and
chemical activation (17). In physical activation, a raw material
is first carbonized and the carbonized material is then acti-
vated by steam, carbon dioxide, air, or their mixture. Physical
and/or chemical activation can be applied to the precursor.
Physical activation involves carbonization of a carbonaceous
material followed by activation in the presence of activating
agents such as CO2 or steam. In chemical activation, carboniza-
tion and activation occurs simultaneously, and raw material is
impregnated with activating agents. The most commonly used
activating agents are ZnCl2 , H3 PO4 , KOH, K2 CO3, etc. Then
the impregnated material is heated in the absence of oxygen
(17).
ZnCl2 is one of the most widely used agents for the chemi-
cal activation of a carbonaceous material. Chemical activation
using ZnCl2 produces high surface area and more porous acti-
vated carbons, and thus provides high adsorption capacity.
ZnCl2 acts as a dehydrating agent promoting the decomposition
of carbonaceous material during the pyrolysis process, restricts
the formation of tar, and increases the carbon yield (18).
 PREPARATION OF HIGH SURFACE AREA ACTIVATED CARBON FROM Elaeagnus angustifolia SEEDS
Often combinations of chemical activation followed by
physical activation methods are employed to improve the char-
acteristics of activated carbon, such as surface area and pore
volume (19).
In comparison with physical activation, there are signifi-
cant advantages of chemical activation. Chemical activation
offers several advantages, which include single-step activation,
low activation temperatures, low activation time, higher yields,
and better porous structure. Chemical agents act as dehydra-
tion agents and they may restrict the formation of tar during
carbonization (18).
Elaeagnus angustifolia, commonly called silver berry,
oleaster, Russian olive, or wild olive, is a species of Elaeagnus,
native to western and central Asia, from southern Russia and
Kazakhstan to Turkey and Iran. Owing to the ligneous charac-
ter of Elaeagnus angustifolia seeds, abundance, and low cost,
the above-referred residue is suitable for use as a raw material
for the preparation of activated carbons.
In the previous study, Elaeagnus angustifolia seeds have
been proposed as an efficient raw precursor for preparation of
activated carbon via ZnCl2 and two-step pyrolysis in air (11).
The present work explores the preparation of high quality acti-
vated carbon including high surface area and more porous acti-
vated carbon from Elaeagnus angustifolia seeds using relatively
low activation temperature. Textural, functional, and surface
characterization of the prepared adsorbent was performed.
MATERIALS AND METHODS
Materials
EAS was collected in the Malatya province of Turkey. EAS
was washed several times with tap water and then with distilled
de-ionized water to remove impurities and salts. It was dried
by heating at 80◦ C overnight. The dried EAS was ground in
a mortar and sieved into a size of −500 + 125. The obtained
material was stored in sealed containers for experimentation.
Active Carbon Preparation
5 g of dried EAS was well mixed with 25 mL of ZnCl2
solution of different impregnation ratios with concentrations
of 30, 50, 90, 150, and 200% for 24 and 48. The carboniza-
tion of samples was carried out in a vertical electric furnace.
The carbonization process was carried out in an inert atmo-
sphere using nitrogen gas of 99.9% purity The furnace was
heated at constant rate of 5◦ C/min and held at different car-
bonization temperatures (400–600◦ C) for different carboniza-
tion times (30–90 min). At the end of activation time, the
carbonized samples were withdrawn from the furnace and
allowed to cool. Then, the samples were thoroughly washed
with 0.5 M hydrochloric acid. Subsequently, the samples were
rinsed sequentially with warm distilled water, followed by cold
distilled water, until the pH of the wash solution fell in the
range of 6-6.5. The resultant samples were dried at 105◦ C
887
in the oven for 24 hours. Finally, the samples were stored in
tightly closed bottles.
Sample Characterization
Iodine test is a test method that covers the relative adsorption
capacity for its simplicity and a rapid assessment of activated
carbon quality by the adsorption of iodine from aqueous solu-
tion. The iodine number is a relative indicator of porosity in an
activated carbon and may be used as an approximation of sur-
face area for activated carbons. The iodine number is defined
as the amount of iodine adsorbed by 1 g of carbon at the mg
level. The iodine adsorption capacity was determined from the
titration of the filtrate with a Na2 S2 O3 solution (20).
The morphologies of the samples were characterized by
using a scanning electron microscope. SEM (Zeiss EVO
50 Model) instrument with a 3 kV accelerating voltage was used
to characterize the morphology of activated carbon which was
dried overnight at approximately 105◦ C under vacuum before
SEM analysis.
The BET surface area and porous property of EAS activated
carbon were determined by nitrogen adsorption/desorption
isotherms at 77 K using a surface area analyzer (Quantachrome
Corporation, USA). Samples were degassed under vacuum at
200◦ C for 2 h. The specific surface area was derived from the
BET theory. The BET surface area, total pore volume, and aver-
age pore diameter are obtained by applying the BET equation
to N2 adsorption. The micropore volume was evaluated by the
t-plot method. The pore size distribution was obtained by DA
method.
The surface functional groups of EAS activated carbon were
recorded by the KBr technique using a FTIR spectrometer.
FTIR spectra were recorded between 4000 and 400 cm−1 by
using Model Perkin Elmer 1100 Spectrophotometer. The trans-
mission spectra of the samples were recorded by using the KBr
pallet containing 0.1% of sample.
TGA and differential thermogram (DTG) were performed to
analyze the thermal degradation characteristics of the activated
carbon. The weight loss was calculated as a function of temper-
ature, using a Perkin Elmer instrument. Approximately 5 mg
activated carbon were placed in a platinum crucible on the pan
of a microbalance, then heated between 20 and 900◦ C at a heat-
ing rate of 10◦ C /min, with nitrogen flow rate of 20 mL/min,
and constantly weighed.
RESULTS AND DISCUSSION
Effect of Activation Temperature
The iodine values of activated carbons prepared with the
ZnCl2 percentage of 150% for 48 h impregnation time and
30 min activation time are shown in Fig. 1. The iodine num-
ber increases gradually from 400◦ C to 500◦ C and it starts
to decrease at 600◦ C. As temperature increases, a number of
metallic zinc were produced, which may induce more pores,
hence the specific surface area was improved. However, higher
888 Ö. ŞAHIN ET AL.

1380 1400
1370 1200
1360

Iodine number (mg/g)

Iodine number (mg/g)

1000
1350
1340 800

1330 600
1320
400
1310
200
1300
1290 0
300 350 400 450 500 550 600 650 0 50 100 150 200 250
Activation temperature (°C) ZnCl2 concentration

FIG. 1. Effect of activation temperature on the production of activated carbon.
temperature may lead to the pores erosion because of excessive
gases overflow. The highest iodine value was 1367 mg/g devel-
oped at an activation temperature of 500◦ C. At temperature
beyond 500◦ C, the surface area decreases which may be due
to the collapse of micropores formed during previous stages.
Effect of Impregnation Ratio and Time
Figures 2 and 3 clearly show that the ZnCl2 percentage is an
important parameter, which affects the iodine values. Figure 2
shows the iodine values of activated carbon prepared at car-
bonization temperature of 600◦ C, activation time of 30 min,
and impregnation time of 24 h, while the ZnCl2 percentage
was varied from 30 to 200%. It can be seen that iodine values
increase continuously with the increasing ZnCl2 percentage,
until reaching a maximum at ZnCl2 percentage of 90%. Then,
iodine values decreased with the increasing ZnCl2 percentage
from 90 to 200%. The highest iodine value was 1296 mg/g
developed at ZnCl2 percentage of 90%. Figure 3 shows the
iodine values of activated carbon prepared at carbonization tem-
perature of 600◦ C, activation time of 30 min and impregnation
time of 48 h, while the ZnCl2 percentage was varied from 30 to
200%. The results show that the iodine values of the activated
1400
FIG. 3. Effect of impregnation ratio on the production of activated carbon the
activation temperature (500◦ C), activation time (60 min), impregnation time
(48 h).
carbon prepared from EAS increased from 450 to 1311 mg/g
with increasing the ZnCl2 percentage from 30 to 150%. The
increase in iodine values is due to the development of pores
and increased porosity in the carbons. After a ZnCl2 percent-
age of 200%, it is clearly seen that there is a low decrease from
1311 to 1202 mg/g. This was possibly because of increasing in
ZnCl2 concentration reaction that may cause a part of the micro-
pore structure to be destroyed by pores collapsing. In addition,
data provided in Fig. 5 show that iodine values obtained with
the impregnation time of 48 h compared to impregnation time
of 24 h carbon increased, as due to the more numerous pores
formed, when the impregnation time increased.
Effect of Activation Time
The effect of activation time on iodine number is illus-
trated in Fig. 4. The activation temperature (500◦ C), the
ZnCl2 percentage of 150%, and impregnation time of 48 h
were set and the impregnation time was varied from 30 to
90 min. The iodine number increased gradually from 1365 to
1445 mg/g with increasing the activation time from 30 to
60 min, and then it decreased from 1445 to 1395 mg/g
with increasing the activation time from 60 to 90 min,

1200
1465
Iodine number (mg/g)

1000 1455

800 1445
Iodine number (mg/g)

1435
600 1425
400 1415
1405
200
1395
0 1385
0 50 100 150 200 250 1375
ZnCl2 concentration 1365
20 30 40 50 60 70 80 90 100
FIG. 2. Effect of impregnation ratio on the production of activated carbon the Activation time (°C)
activation temperature (600◦ C), activation time (30 min), impregnation time
(24 h). FIG. 4. Effect of activation time on the production of activated carbon.
 PREPARATION OF HIGH SURFACE AREA ACTIVATED CARBON FROM Elaeagnus angustifolia SEEDS 889

FIG. 6. Pore size distribution of the prepared activated carbon.

FIG. 5. Nitrogen adsorption isotherm on the activated carbon prepared based

the activation temperature (500◦ C), activation time (60 min), impregnation time
(48 h), and ZnCl2 percentage of 150%.
indicating that longer activation time caused some of the
pores to enlarge or even collapse.
BET Analysis and Pore Size Distribution
The nitrogen adsorption-desorption isotherm is commonly
used for the analysis of the physical properties. Figure 5 shows
the nitrogen adsorption-desorption isotherms at 77 K on the
activated carbon prepared based the impregnation time (48 h),
activation temperature (500◦ C), activation time (60 min), and
the ZnCl2 percentage of 150%. The BET surface area of acti-
vated carbon obtained from activation of EAS were bigger than
those reported previously, including Elaeagnus angustifolia
seeds via ZnCl2 and two-stage pyrolysis in air. The maximum
BET surface area reached in this study is 1836 m2 /g. The
maximum BET surface area reached in previously our study
was 697 m2 /g. Type I isotherm usually reflects the presence of
microporous structure.
Total pore volume was 1.03 cc/g. Average pore size was
1.12 nm. The maximum micropore volume was 0.12 cc/g. BJH
pore volume and pore radius for the best activated carbon was
0.16 cc/g and 1.53 nm.
The pore size distribution is a relative abundance of each
pore size in a specific pore volume, which was determined
using Dubinin–Astakhov (DA) pore size distribution method
for EAS. The DA method is often used to evaluate the micro-
pores of activated carbons. The DA method adsorption pore
radius is shown in Fig. 6. The result detected the sharpest peak
with an adsorption pore radius of 0.89 nm. The DR method
micropore half pore width is 1.64 nm.
A comparison of the characteristics of the activated carbons
due to the present study with other literature reported values for
the EAS based precursor are listed in Table 1. It can be observed

TABLE 1
A comparison of the characteristics of the activated carbons with other literature reported values
BET Surface Iodine number
Raw material Treatment Method Area(m2 /g) (mg/g) References
Acorn shell Chemical, ZnCl2 One-step pyrolysis/activation 1289 1209 5
Acorn shell Physical, CO2 Two-step physical method 1779 1152 6
Barley husks Chemical, ZnCl2 One-step pyrolysis/activation 811 901 12
Nutshells of Chemical, ZnCl2 one-step pyrolysis/activation 712 1122 13
Sterculia alata
Corn cob Physical, Steam Steam activation method 980 665 8
Corn cob Chemical, KOH One-step activation method 1600 1282 8
Safflower seed Chemical, ZnCl2 One-step activation method 801 − 9
press cake
The vetch Chemical, ZnCl2 Two-step Chemical method 1287 1004 10
Elaeagnus Chemical, ZnCl2 Two-step Chemical method in air 697 1009 11
angustifolia seeds
Elaeagnus Chemical, ZnCl2 One-step Chemical method in N2 1836 1445 This study
angustifolia seeds
890 Ö. ŞAHIN ET AL.

FIGS. 7a, b, c, d. Scanning electron micrographs of the activated carbon prepared the activation temperature (500◦ C), activation time (60 min), impregnation
time (48 h), and ZnCl2 percentage of 150%.

from the data provided in the table that the BET surface area
and iodine number due to the present study is much higher than
those reported using physical or chemical activation.

Textural Characterization by SEM

The SEM micrographs of activated carbon were presented
in Figs. 7 a-d. According to the SEM images, the produced
activated carbon have highly porous structure, which appeared
to have a roughly texture with heterogeneous surface structure.
The white spheres in the images of the sample may be attributed
to the presence of zinc salt residues. It seems that the cavities on
the surface of the carbon resulted from the evaporation of ZnCl2
during carbonization, leaving the space previously occupied by FIG. 8. The FT-IR spectra of the activated carbon prepared based the activa-
the ZnCl2 . tion temperature (500◦ C), activation time (60 min), impregnation time (48 h),
and ZnCl2 percentage of 150%.

FTIR Spectroscopy for Surface Functional Group Analysis

The FTIR spectra of EAS activated carbon were recorded in
the range of 4000–400 cm−1 (Fig. 8). The broad O–H stretch-
ing vibrations at 3000-4000 cm−1 are assigned to the hydroxyl
groups present in alcohols, phenols, and carboxylic acids. The
bands at around 1800 cm−1 are due to the stretching of C-O
vibration. The peak at 1574 cm−1 indicates the C–O stretch-
ing mode of the carbonyls, carboxylic acids, and lactones. The
peak at 1152 cm−1 could be attributed to C—O stretching alco-
hol, carboxylic acid, ether, and ester. The peak at 871 cm−1 was
ascribed to C–H bending, while the peak at 745 was ascribed to
the O–H group.
Thermogravimetry Analysis
The thermal behavior of EAS was observed by TG/DTG
in N2 gas environment (Fig. 9). TG curves show that the
weight of EAS decreased gradually with temperature. The first
mass loss for temperatures up to 200◦ C can be attributed to
 PREPARATION OF HIGH SURFACE AREA ACTIVATED CARBON FROM Elaeagnus angustifolia SEEDS
FIG. 9. The thermal behavior of EAS.
moisture elimination that was originally contained in the EAS.
In the 200–500◦ C temperature range, the observed weight loss
difference of the sample is a relevant pyrolysis property of
the EAS components, typically cellulose, hemicellulose, and
lignin, which was considered to be due to the vaporization of
volatile organic compounds. Above 400◦ C, the mass loss may
be attributed to the reaction between the activating agent and
carbonaceous residue.
CONCLUSIONS
Activated carbon from EAS by one-stage chemical acti-
vation was prepared using ZnCl2 in N2 . The effects of the
activation temperature, impregnation time, activation time, and
the impregnation ratio on the surface of activated carbon were
investigated. The experimental results showed that activation
temperature, activation, and impregnation ratio were highly
effective on iodine number of activated carbons. The highest
iodine number was achieved as 1445 mg/g. BET surface area
evaluated using nitrogen adsorption isotherm corresponds to
1836 m2 /g, with the total pore volume of 1.03 cc/g. SEM
micrographs of activated carbon shown that EAS appeared to
have a rough texture with heterogeneous surface structure with
cavities on its surface.
REFERENCES
1. Saka, C., Şahin, Ö., Küçük, M. M. (2012) Application of agricultural and
forest waste adsorbents for removal of lead (II) from contaminated water.
Inter. J. Environ. Sci. Technol. 9: 379–394.
2. Greiner, E. O. C., Kälin, T., Inoguchi, Y. (2010) Activated Carbon,
Chemical Economics Handbook; SRI Consulting, p. 5.
3. Dolas, H., Şahin, Ö., Saka, C., Demir, H. (2011) A new method on pro-
ducing high surface area activated carbon: The effect of salt on the surface
891
area and the pore size distribution of activated carbon prepared from
pistachio shell. Chem. Eng. J. 166: 191–197.
4. Özdemir, M., Bolgaz, T., Saka, C., Şahin, Ö. (2011) Preparation and char-
acterization of activated carbon from cotton stalks in a two-stage process.
J. Anal. Appl. Pyrol. 92: 171–175.
5. Saka, C. (2012) BET, TG-DTG, FTIR, SEM, iodine number analysis and
Preparation of activated carbon from acorn shell by chemical activation
with ZnCl2 . J. Anal. Appl. Pyrol. 95: 21–24.
6. Sahin, O., Saka, C. (2013) Preparation and characterization of activated
carbon from acorn shell by physical activation with H2 O-CO2 in two-step
pretreatment. Biores. Technol. 136: 163–168.
7. Kalderis, D., Bethanis, S., Paraskeva, P., Diamadopoulos, E. (2008)
Production of activated carbon from bagase and rice husk by a sin-
glestage chemical activation at low retention times. Biores. Technol. 99:
6809–6816.
8. Song, M., Jin, B., Xiao, R., Yang, L., Wu, Y., Zhong, Z., Huang, Y. (2013)
The comparison of two activation techniques to prepare activated carbon
from corn cob. Biomass and Bioenergy 48: 250–256.
9. Angın, D., Altintig, E., Kose, T. E. (2013) Influence of process parameters
on the surface and chemical properties of activated carbon obtained from
biochar by chemical activation. Biores. Technol. 148: 542–549.
10. Ceyhan, A. A., Şahin, Ö., Saka, C., Yalçın, A. (2013) A novel thermal
process for activated carbon production from the vetch biomass with air
at low temperature by two-stage procedure. J. Anal. Applied Pyrol. 104:
170–175.
11. Ceyhan, A. A., Şahin, Ö., Baytar, O., Saka, C. (2013) Surface and porous
characterization of activated carbon prepared from pyrolysis of biomass
by two-stage procedure at low activation temperature and its adsorption
of iodine. J. Anal. Applied Pyrol 104: 378–383.
12. Loredo-Cancino, M., Soto-Regalado, E., Cerino-Cordova, F.J., Garcia-
Reyes, R. B., Garcia-Leon, A. M., Garza-Gonzalez, M. T. (2013)
Determining optimal conditions to produce activated carbon from barley
husks using single or dual optimization. J Environ. Manag. 125: 117–125.
13. Mohanty, K., Das, D., Biswas, M. (2006) Preparation andcharacterization
of activated carbons from sterculia alata nutshell by chemical activation
with zinc chloride to remove phenol from wastewater. Adsorption 12:
119–132.
14. Foo, K.Y., Hameed, B. H. (2012) Mesoporous activated carbon from wood
sawdust by K2 CO3 activation using microwave heating. Biores. Technol.
111: 425–32.
15. Foo, K. Y., Hameed, B. H. (2012) Potential of jackfruit peel as precursor
for activated carbon prepared by microwave induced NaOH activation.
Biores. Technol. 111: 143–150.
16. Foo, K. Y., Hameed, B. H. (2011) Utilization of rice husks as a feed-
stock for preparation of activated carbon by microwave induced KOH and
K2 CO3 activation. Biores. Technol. 102: 9814–9817.
17. Ahmadpour, A., Do, D. D. (1996) The preparation of active carbons from
coal by chemical and physical activation. Carbon 34: 471–479.
18. Smisek, M., Cerny, S. (1970) Active Carbon Manufacture, Properties and
Applications; Elsevier: New York.
19. Azevedo, D. C. S., Araujo, J. C. S., Bastos-Neto, M., Torres, A. E. B.,
Jaguaribe, E. F., Cavalcante, C. L. (2007) Microporous activated carbon
prepared from coconut shells using chemical activation with zinc chloride.
Microporous and Mesoporous Materials 100: 361–364.
20. ASTM (2006). D4607 - 94, Standard Test Method for Determination of
Iodine Number of Activated Carbon West Conshohocken, PA, ASTM
International.
21. Gürses, A., Doğar, Ç., Karaca, S., Açikyildiz, M., Bayrak, R. (2006)
Production of granular activated carbon from waste Rosa caninasp.
seeds and its adsorption characteristics for dye. J. Hazard. Mater. 131:
254–259.
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